Reductive leaching of manganese from low-grade pyrolusite ore in sulfuric acid using pyrolysis-pretreated sawdust as a reductant

Manganese (Mn) leaching and recovery from low-grade pyrolusite ore were studied using sulfuric acid (H₂SO₄) as a leachant and pyrolysis-pretreated sawdust as a reductant. The effects of the dosage of pyrolysis-pretreated sawdust to pyrolusite ore, the concentration of sulfuric acid, the liquid/solid ratio, the leaching temperature, and the leaching time on manganese and iron leaching efficiencies were investigated. Analysis of manganese and iron leaching efficiencies revealed that a high manganese leaching efficiency was achieved with low iron extraction. The optimal leaching efficiency was determined to be 20wt% pyrolysis-pretreated sawdust and 3.0 mol/L H₂SO₄ using a liquid/ solid ratio of 6.0 mL/g for 90 min at 90℃. Other low-grade pyrolusite ores were tested, and the results showed that they responded well with manganese leaching efficiencies greater than 98%.     

Preparation of manganese sulfate from low-grade manganese carbonate ores by sulfuric acid leaching

In this study, a method for preparing pure manganese sulfate from low-grade ores with a granule mean size of 0.47 mm by direct acid leaching was developed. The effects of the types of leaching agents, sulfuric acid concentration, reaction temperature, and agitation rate on the leaching efficiency of manganese were investigated. We observed that sulfuric acid used as a leaching agent provides a similar leaching efficiency of manganese and superior selectivity against calcium compared to hydrochloric acid. The optimal leaching conditions in sulfuric acid media were determined; under the optimal conditions, the leaching efficiencies of Mn and Ca were 92.42% and 9.61%, respectively. Moreover, the kinetics of manganese leaching indicated that the leaching follows the diffusion-controlled model with an apparent activation energy of 12.28 kJ·mol-1. The purification conditions of the leaching solution were also discussed. The results show that manganese dioxide is a suitable oxidant of ferrous ions and sodium dimethyldithiocarbamate is an effective precipitant of heavy metals. Finally, through chemical analysis and X-ray diffraction analysis, the obtained product was determined to contain 98% of MnSO₄·H₂O.     

硫酸中香蕉皮还原低品位锰矿的浸出行为及动力学模型

Manganese was leached from a low-grade manganese ore (LGMO) using banana peel as the reductant in a dilute sulfuric acid medium. The effects of banana peel amount, H₂SO₄ concentration, reaction temperature, and time on Mn leaching from the complex LGMO were studied. A leaching efficiency of ~98% was achieved at a leaching time of 2 h, banana peel amount of 4 g, leaching temperature of 120°C, manganese ore amount of 5 g, and sulfuric acid concentration of 15vol%. The phase, microstructural, and chemical analyses of LGMO samples before and after the leaching process confirmed the successful leaching of manganese. Furthermore, the leaching process followed the shrinking core model and the leaching rate was controlled by a surface chemical reaction (1 ? (1 ? x)1/3 = kt) mechanism with an apparent activation energy of 40.19 kJ·mol?1.     

响应面法优化葡萄糖还原浸出半氧化锰矿的研究

采用响应面法优化葡萄糖还原浸出半氧化锰矿的工艺,以锰浸出率为响应值,对硫酸用量/矿量、葡萄糖用量/矿量、氟化铵用量/矿量和浸取时间四因素进行建模。结果表明,这些因素与锰浸出率的关系符合二次模型,各个因素对锰浸出率影响均极其显著,各个因素的二次方以及硫酸用量/矿量与葡萄糖用量/矿量的交互作用对锰浸出率影响较显著。最优工艺条件为：硫酸用量/矿量0.880 g/g、葡萄糖用量/矿量0.059 g/g、氟化铵用量/矿量0.04 g/g、浸取时间6 h。在此条件下,锰浸出率为93.09%,与模型预测值93.18%无显著差异,而相同条件下未加氟化铵的锰浸出率为82.37%。     

Effect of desliming on the magnetic separation of low-grade ferruginous manganese ore

In the present investigation, magnetic separation studies using an induced roll magnetic separator were conducted to beneficiate low-grade ferruginous manganese ore. The feed ore was assayed to contain 22.4% Mn and 35.9% SiO₂, with a manganese-to-iron mass ratio (Mn:Fe ratio) of 1.6. This ore was characterized in detail using different techniques, including quantitative evaluation of minerals by scanning electron microscopy, which revealed that the ore is extremely siliceous in nature and that the associated gangue minerals are more or less evenly distributed in almost all of the size fractions in major proportion. Magnetic separation studies were conducted on both the as-received ore fines and the classified fines to enrich their manganese content and Mn:Fe ratio. The results indicated that the efficiency of separation for deslimed fines was better than that for the treated unclassified bulk sample. On the basis of these results, we proposed a process flow sheet for the beneficiation of low-grade manganese ore fines using a Floatex density separator as a pre-concentrator followed by two-stage magnetic separation. The overall recovery of manganese in the final product from the proposed flow sheet is 44.7% with an assay value of 45.8% and the Mn:Fe ratio of 3.1.     

A primary study of simultaneous leaching of silver containing manganese ore and a sphalerite concentrate

It is demonstrated that a low grade, silver containing manganese deposit can be exploited by reaction with a ZnS concentrate. In the process, Mn（IV） is reduced to Mn（II） and the ZnS converted to ZnSO4. In the process, Mn and Zn are solubilized. By studying the effects of quantity of reducing agent and sulfuric acid added and of time, temperature and liquid-to-solid ratio on the leaching process, the optimum technological conditions have been achieved un- der which the amount of manganese leached was 98 %. The silver can be removed from remaining solids by adding ammonia liquor. Then by adding hydrazine hydrate, sponge silver with purity up to 99 % can be obtained with a recovery of 87 %.     

改善原地溶浸工艺中矿石破碎质量的力学机理

通过改善矿石的破碎质量,提高矿堆的渗透性,使原地溶浸法开采稳固性和渗透性极差的低品位铜镍矿石成为可能.依据矿石中缺陷存在的情况,应用断裂动力学和损伤力学的观点,着重分析了爆炸应力波能量加载对矿石破裂、损伤行为产生的影响;对矿石块体中贮存爆破动能加载,致使块体产生破裂或损伤的行为进行了探讨.此外,对浸蚀裂解与作用在爆堆上的地压能在破裂或损伤过程中所起的辅助作用进行了讨论.给出了应用中深孔挤压爆破技术,原地崩落低品位铜镍矿石,形成溶浸矿堆的一些相应相关技术参数.分析结果表明采用合理的爆破技术,可以改善应力波和爆破动能的加载条件,能提高矿石块体的破碎质量及累积损伤程度;借助于浸蚀裂解与地压能的作用,可进一步改善堆浸矿石的块体分布,提高溶浸液与有用组分的接触和被浸出的机会.     

碱性氧化铜矿产氨菌浸出特性

为了研究碱性氧化铜矿产氨菌浸出特性,分析了产氨菌浸矿过程对矿石的作用.将云南某矿的碱性氧化铜矿置于含菌培养液、去菌培养液和氨水等5种浸矿溶液中,在同一条件下进行摇瓶浸矿实验,剖析溶液中各可能的浸矿因子.研究结果表明:产氨菌产氨能力较强,尿素培养液中氨质量浓度最大达8.93 g·L-1;产氨量与细菌含量呈正相关关系,细菌含量越高,产氨量越大;产氨菌主要通过产氨间接浸矿,此外产氨菌和其代谢产物都能直接作用于矿石,浸矿能力细菌产氨>细菌>细菌代谢产物,三者比值约为12:5:4.     

Optimization of reaction conditions for the electroleaching of manganese from low-grade pyrolusite

In the present study, a response surface methodology was used to optimize the electroleaching of Mn from low-grade pyrolusite. Ferrous sulfate heptahydrate was used in this reaction as a reducing agent in sulfuric acid solutions. The effect of six process variables, including the mass ratio of ferrous sulfate heptahydrate to pyrolusite, mass ratio of sulfuric acid to pyrolusite, liquid-to-solid ratio, current density, leaching temperature, and leaching time, as well as their binary interactions, were modeled. The results revealed that the order of these factors with respect to their effects on the leaching efficiency were mass ratio of ferrous sulfate heptahydrate to pyrolusite > leaching time > mass ratio of sulfuric acid to pyrolusite > liquid-to-solid ratio > leaching temperature > current density. The optimum conditions were as follows: 1.10:1 mass ratio of ferrous sulfate heptahydrate to pyrolusite, 0.9:1 mass ratio of sulfuric acid to pyrolusite, liquid-to-solid ratio of 0.7:1, current density of 947 A/m2, leaching time of 180 min, and leaching temperature of 73℃. Under these conditions, the predicted leaching efficiency for Mn was 94.1%; the obtained experimental result was 95.7%, which confirmed the validity of the model.     

硫氧混合铅锌矿中锌的氧化氨浸动力学

常压低温条件下在NH3-(NH4)2 SO4体系中使用过硫酸铵作为氧化剂对硫氧混合铅锌矿中的锌进行浸出实验,系统研究了搅拌速度、浸出剂浓度、氧化剂浓度与温度对于锌浸出率的影响.结果表明,在最优条件下锌的浸出率可达93.2%,且浸出过程中几乎没有其他离子进入溶液,实现了锌的选择性高效浸出,从而简化了后续的浸出液净化与材料制备过程.动力学研究表明,硫氧混合铅锌矿中锌的氧化氨浸过程遵循固体产物层扩散控制的未反应核收缩模型,浸出反应的表观活化能为17.89 kJ·mol-1.     

锰矿浸渣中可溶锰离子的稳定化处理研究

为了解决日益严重的锰矿浸渣污染问题,采用在锰矿浸渣中添加硅酸钠为固化剂,研究锰矿浸渣中可溶锰离子的稳定化效果。通过正交实验和单因素实验,考察了反应温度、反应时间、液固比、p H值、硅酸钠添加量等因素对可溶锰离子稳定化效果的影响。结果表明:硅酸钠的用量对可溶锰离子稳定化效果的影响最大,较适宜的稳定化条件为:反应温度30℃,反应时间15 min,液固比5∶1,p H值8,硅酸钠用量0.5 g。在此条件下,20.00 g锰矿浸渣中的可溶锰离子固化率达96.80%,通过浸出毒性测试得到滤液中锰残余浓度为0.99 mg/L,完全符合GB8978-96《污水综合排放标准》。     

玉米秸秆还原浸出高铁低品位锰矿研究

采用"玉米秸秆硫酸预处理—浸出"工艺处理含Mn 9.63%(质量分数)的朝阳锰矿.通过试验考察用硫酸对玉米秸秆进行预处理的时间、秸秆用量、温度、硫酸浓度和浸出温度对锰浸出率的影响.试验表明,在秸秆用量2.5 g、时间10 min、硫酸浓度1.2 mol/L、温度80℃时预处理秸秆,浸出温度为90℃的条件下,锰的浸出率达92%,杂质铁溶出率仅为20%.玉米秸秆处理前后FTIR分析结果表明,对秸秆进行硫酸预处理能够破坏难降解的木质素结构,有利于提高锰的浸出效果.     

Reductive recovery of manganese from low-grade manganese dioxide ore using toxic nitrocellulose acid wastewater as reductant

The hydrometallurgical strategy of extracting Mn from low-grade Mn ores has attracted attention for the production of electrolytic manganese metal (EMM). In this work, the reductive dissolution of low-grade MnO₂ ores using toxic nitrocellulose acidic wastewater (NAW) as a reductant was investigated for the first time. Under the optimized conditions of an MnO₂ ore dosage of 100 g·L-1, an ore particle size of -200 mesh, concentrated H₂SO₄-to-NAW volume ratio of 0.12, reaction temperature of 90℃, stirring speed at 160 r·min-1, and a contact time of 120 min, the reductive leaching efficiency of Mn and the total organic carbon (TOC) removal efficiency of NAW reached 97.4% and 98.5%, respectively. The residual TOC of 31.6 mg·L-1 did not adversely affect the preparation of EMM. The current process offers a feasible route for the concurrent realization of the reductive leaching of Mn and the treatment of toxic wastewater via a simple one-step process.     

低品位黄铜矿的磁场强化细菌浸出

针对低品位黄铜矿进行了磁场强化细菌浸出实验研究。重点研究了磁场对细菌生长和细菌浸矿的影响。实验结果表明,磁化处理后的培养基能促进细菌的生长繁殖,提高其氧化活性,用于浸矿试验,提高了低品位黄铜矿中铜和铁的浸出率。磁场强化细菌浸出的可能机理是通过改变水的结构,促进氧气在水中的溶解,提高矿石成分的溶解性,增强细菌细胞生物膜的穿透性。     

玉米秸秆和稻草-硫酸还原浸出低品位软锰矿

研究了以低品位软锰矿为原料,用玉米秸秆和稻草为混合还原剂,在硫酸介质中还原浸出锰的效果.通过单因素实验确定了玉米秸秆和稻草-硫酸还原浸锰的适宜工艺条件,该适宜工艺条件如下:软锰矿粒径为109μm,玉米秸秆和稻草的质量比为1∶1.5,玉米秸秆和稻草还原剂与软锰矿的质量比为3∶10,硫酸浓度为3.0 mol/L,液固比为10 m L/g,反应温度为90℃,反应时间为80 min.在适宜的浸出工艺条件下,软锰矿中锰的浸出率可达97%以上,锰的浸出效果较好.     

Hydrometallurgical leaching and kinetic modeling of low-grade manganese ore with banana peel in sulfuric acid

Manganese was leached from a low-grade manganese ore(LGMO) using banana peel as the reductant in a dilute sulfuric acid medium. The effects of banana peel amount, H_2SO_4 concentration, reaction temperature, and time on Mn leaching from the complex LGMO were studied. A leaching efficiency of ～98% was achieved at a leaching time of 2 h, banana peel amount of 4 g, leaching temperature of 120°C,manganese ore amount of 5 g, and sulfuric acid concentration of 15 vol%. The phase, microstructural, and chemical analyses of LGMO samples before and after the leaching process confirmed the successful leaching of manganese. Furthermore, the leaching process followed the shrinking core model and the leaching rate was controlled by a surface chemical reaction(1-(1-x)~(1/3)=kt) mechanism with an apparent activation energy of 40.19 k J·mol~(-1).     

铬渣柱浸生物解毒的研究

针对长沙铬盐厂铬渣污染的现状及铬渣的性质,进行了细菌柱浸解毒铬渣的实验。研究结果表明,实验前需将铬渣制成颗粒,解毒工艺的最佳粒径为4~8mm;最佳pH为10.0;最佳温度为30℃。在最佳工艺条件下,铬渣浸出液中Cr（Ⅵ）的浓度由250.6mg/L降为0mg/L,达到国家规定的废水排放标准;解毒后渣的浸出毒性为0.4mg/L,低于国家固体废物浸出毒性标准所规定的1.5mg/L。     

复吹转炉锰矿直接合金化热力学模型研究

基于某钢厂铁水、废钢和造渣料等的成分得出转炉炼钢的渣量计算模型,根据热力学原理得出锰的收得率和终点锰含量的预报模型。对模型研究结果表明,提高终点出钢温度、渣碱度、锰矿品位和铁水Mn含量,降低终渣含量及渣中FeO含量,可显著提高Mn的收得率和终点Mn含量。     

天然低品位氧化锰矿生产活性二氧化锰

为了改变优质电池原料短缺的状况和充分利用低品位锰矿资源 ,研究了天然低品位二氧化锰矿在添加少量无污染添加剂的条件下 ,在 71 0℃下焙烧 2h ,可使矿石中MnO2 转化为Mn2 O3 .其转化率达 99 5 %以上 .同时对焙烧产物进行岐化反应所用的酸介质、酸用量和反应时间与歧化作用的关系进行了研究 .并对氯酸钠氧化歧化液中Mn2 的氧化效果进行了分析 ,提出了分步氧化歧化液中Mn2 的新工艺 .     

用碘--碘化物溶液从含金矿石中提取金

考虑不同电解液中影响金溶解的热力学因素,由热力学计算结果绘制25℃时的金--碘--水体系的Eh-pH图,分析得到金-碘系统在水环境中的稳定区域：pH=0～14;结合对碘化浸金热力学、动力学的分析,在浸金实验的基础上,分析碘浸出金的机理;以碘-碘化物为浸出剂,实验研究含碳矿石中金的溶解,讨论金萃取的反应时间、碘-碘化物质量分数、pH对浸出的影响,并与氰化物的浸出结果进行对比;探讨从浸出液中回收金及碘的再生方法.所得金浸出的合理条件为：碘的质量分数在0.8%～1.0%,n（12）：n（I^-）=1：8～1：10,助氧化剂双氧水质量分数在1%～2%,浸出时间为4h,液固比在3：1～5：1,浸出温度为常温,矿浆为中性或酸性.金的浸出率可达93%以上,浸出液中的金和碘均可用电解方法回收.分析证明,在达到相同浸出率的情况下,与氰化法相比,碘化法浸出时间短、综合成本低.